马来松香酸和纳米氧化铝颗粒协同稳定具有pH响应性的Pickering乳液

doi:10.6023/A21120567

摘要/Abstract

使用有机颗粒稳定Pickering乳液受到越来越多的关注, 润湿性可调的有机颗粒且结合纳米无机颗粒协同稳定不同类型的Pickering乳液却鲜有报道. 系统研究了基于具有多羧酸基团的松香基衍生物马来松香(MPA)与纳米Al₂O₃颗粒在不同pH条件下形成的乳液类型及相关机理. 研究发现, 在单一MPA颗粒体系条件下, pH可以诱导乳液的类型由W/O Pickering乳液到O/W Pickering乳液, 到最后O/W乳液的转变, MPA的亲水性随着pH升高而增强是该乳液转变的原因. 当纳米Al₂O₃颗粒加入到MPA中后, 吸附在MPA颗粒上的亲水性Al₂O₃导致MPA颗粒亲水性增加, 从而可以使W/O Pickering乳液转变为O/W Pickering乳液(pH=1). 当pH=6时, MPA分子与纳米Al₂O₃颗粒同时具有较强的亲水性且分别无法形成稳定的乳液, 但两者的混合体系可以形成稳定的W/O Pickering乳液, 这是因为MPA分子与纳米Al₂O₃颗粒可以在水溶液中形成疏水性较强的络合物. 另外, 研究了MPA浓度及油相体积分数对乳液外观及粒径的影响, 发现随着MPA浓度增加Pickering乳液的粒径逐渐减小, 增加油相的体积分数会引起粒径的增大. 最后, 利用Zeta电势、颗粒在油水界面吸附率、接触角及表/界面张力研究了稳定Pickering乳液的稳定机理, 在油水界面上吸附的类似盔甲状颗粒层及颗粒层之间形成的网状结构是乳液液滴保持稳定的原因. 为Pickering乳液的绿色化制备提供了一种新的途径, 将在化妆品、医药及新材料等领域得到重要应用.

关键词: 马来松香, Pickering乳液, 纳米Al₂O₃颗粒, 相转变, 协同稳定

Using organic particles to stabilize Pickering emulsions has attracted more and more attention. However, Pickering emulsions synergistically stabilized by organic particles with adjustable wettability combined with inorganic particles is rarely reported. Herein, maleopimaric acid (MPA) with multi-carboxylic acid groups and alumina nanoparticles are used to stabilize Pickering emulsions, and the transitions of the type of Pickering emulsions induced by pH and related mechanisms are systematically studied. With the increase of pH, resulting in the change of the type of emulsions from a W/O Pickering emulsion to an O/W Pickering emulsion to an O/W emulsion when only MPA is used. The increase of the hydrophilicity of MPA is the reason for the transformation of the emulsion. When alumina nanoparticles are added to the system, W/O Pickering emulsions can be transformed into O/W Pickering emulsions (pH=1), which is attributed to the increase of the hydrophilicity of MPA particles caused by the adsorption of alumina nanoparticles on the surface of MPA particles. When pH=6, both MPA particles and alumina nanoparticles have strong hydrophilicity and cannot form stable emulsions respectively, but the mixture of the two can form stable W/O Pickering emulsions. It is because that MPA particles and alumina nanoparticles can form hydrophobic complexes in aqueous solution. In addition, the influence of MPA concentration and volume fraction of oil phase on the appearance and droplet size of Pickering emulsion is studied. It is found that the droplet size of Pickering emulsion gradually decreases with the increase of MPA concentration. However, the increase of volume fraction of oil phase will cause the increase of droplet size. Finally, the stability mechanism of Pickering emulsion is studied by the measurement of Zeta potential, adsorption rate of particles at the oil-water interface, three phase contact angle and surface/interface tensions. The armor-like particles layer adsorbed on the oil-water interface and the network structure formed between the particles are the reason for the stability of emulsion droplets. This study provides a new avenue for the green preparation of Pickering emulsions, which will be important applications in the fields of cosmetics, medicine and new materials.

Key words: maleopimaric acid, pickering emulsions, alumina nanoparticles, phase transition, synergistic stable

引用此文

贺续发, 贾康乐, 余龙飞, 刘明杰, 郑小珊, 李欢玲, 辛锦兰, 黄淋佳. 马来松香酸和纳米氧化铝颗粒协同稳定具有pH响应性的Pickering乳液[J]. 化学学报, 2022, 80(6): 765-771.

Xufa He, Kangle Jia, Longfei Yu, Mingjie Liu, Xiaoshan Zheng, Huanling Li, Jinlan Xin, Linjia Huang. pH-Responsive Pickering Emulsions Synergistically Stabilized by Maleopimaric Acid and Alumina Nanoparticles[J]. Acta Chimica Sinica, 2022, 80(6): 765-771.

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图/表 7

图1. 0.5% (w) MPA在不同pH条件下乳液转变示意图(a), 形成的Pickering乳液外观(b)及相应的显微镜图片(c)

Figure 1. Schematic illustration of phase transition of emulsions induced by pH (a), appearance (b) and optical photographs (c) of emulsions stabilized by 0.5% (w) MPA at different pH

图2. 0.5% (w) MPA (a)和0.5% (w) Al2O3 (b)颗粒在不同pH条件下形成的Pickering乳液外观及相应的显微镜图片

Figure 2. Appearance and optical pictures of Pickering emulsions stabilized by 0.5% (w) MPA (a) and 0.5% (w) Al2O3 nanoparticles (b) at different pH

图3. 0.5% (w) Al2O3颗粒与不同浓度的MPA在pH=7时的乳液状态及显微镜图片: (a) 0.0001% (w), (b) 0.001% (w), (c) 0.01% (w)和(d) 0.1% (w)

Figure 3. Appearance and optical pictures of Pickering emulsions stabilized by 0.5% (w) Al2O3 nanoparticles and different concentrations of MPA at pH=7: (a) 0.0001% (w), (b) 0.001% (w), (c) 0.01% (w) and (d) 0.1% (w)

图4. 0.1% (w) MPA和0.5% (w) Al2O3颗粒在pH=7时不同油相体积分数的乳液状态及显微镜图片

Figure 4. Appearance and microscopy pictures of Pickering emulsions stabilized by 0.1% (w) MPA and 0.5% (w) Al2O3 nanoparticles at pH=7 with different oil volume fractions

图5. (a)纳米Al2O3颗粒[0.5% (w)]在不同浓度MPA溶液的Zata电势和(b)纳米Al2O3颗粒[0.5% (w)]在不同MPA浓度下在油水界面上的吸附率

Figure 5. (a) Zeta potential of 0.5% (w) Al2O3 nanoparticles with different concentrations of MPA aqueous solutions. (b) Percentage of adsorbed Al2O3 nanoparticles at the decane-water interface in the Pickering emulsions stabilized by 0.5% (w) Al2O3 nanoparticles with different concentrations of MPA

图6. 在pH=7时, 不同浓度MPA水溶液中油滴在氧化铝板的三相接触角

Figure 6. Three-phase contact angles of oil droplets in different concentrations of MPA aqueous solution on aluminum oxide plate at pH=7

图7. MPA与纳米Al2O3颗粒在不同浓度比pH=7下的表面张力(a和b)和界面张力(c和d)

Figure 7. Surface tensions (a and b) and interfacial tensions (c and d) of decane-water at different concentration ratios of MPA and Al2O3 nanoparticles at pH=7

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